EP0333941B1 - Compositions de haute énergie à liants thermoplastiques coulables - Google Patents

Compositions de haute énergie à liants thermoplastiques coulables Download PDF

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Publication number
EP0333941B1
EP0333941B1 EP19880302462 EP88302462A EP0333941B1 EP 0333941 B1 EP0333941 B1 EP 0333941B1 EP 19880302462 EP19880302462 EP 19880302462 EP 88302462 A EP88302462 A EP 88302462A EP 0333941 B1 EP0333941 B1 EP 0333941B1
Authority
EP
European Patent Office
Prior art keywords
polybutadiene
plasticizer
composition
propellant
binder system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19880302462
Other languages
German (de)
English (en)
Other versions
EP0333941A1 (fr
Inventor
Rodney L. Willer
Robert G. Gleeson
James A. Hartwell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ATK Launch Systems LLC
Original Assignee
Thiokol Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thiokol Corp filed Critical Thiokol Corp
Priority to DE8888302462T priority Critical patent/DE3872380D1/de
Priority to EP19880302462 priority patent/EP0333941B1/fr
Publication of EP0333941A1 publication Critical patent/EP0333941A1/fr
Application granted granted Critical
Publication of EP0333941B1 publication Critical patent/EP0333941B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/005—By a process involving melting at least part of the ingredients

Definitions

  • the present invention is directed to castable thermoplastic binders for high-energy compositions, particularly composite solid rocket propellants.
  • U.S. Patent No. 4,361,526 proposes to use a thermoplastic elastomeric binder which is a block copolymer of a diene and styrene, the styrene blocks providing a meltable crystal structure and the diene blocks imparting rubbery or elastomeric properties to the copolymer.
  • a propellant composition using the copolymer, the copolymer is dissolved in an organic solvent, such as toluene, and the solids and other propellant formulations are added. The solvent is then evaporated, leaving a rubbery solid which may be divided into pellets suitable for casting or other processing.
  • a disadvantage of formulating a propellant composition using a thermoplastic elastomeric binder which must be dissolved in a solvent is that the propellant formulation cannot be cast in a conventional manner, e.g., into a rocket motor casing.
  • solvent-based processing presents problems with respect to solvent removal and recovery.
  • thermoplastic elastomeric binders which can be melted and cast without the need for solvent processing.
  • a melt-cast high energy composition comprising energetic particulate solids dispersed in and spatially immobilized in a binder system having between 25 and 50 weight percent of 1,2 syndiotactic polybutadiene and between 50 and 75 weight percent of a plasticizer miscible with said polybutadiene.
  • the polybutadiene binder system is useful for spatially immobilizing solid particulates, such as fuel material particulates and oxidizer particulates, in a high-energy formulation such as a propellant.
  • the polybutadiene binder is meltable, allowing it to be mixed with other components of the propellant formulation, including the solid particulates and the plasticizer, and is castable, e.g., into a rocket motor shell. No organic solvent is required to prepare or cast the propellant formulation.
  • a method of preparing a high-energy composition comprising mixing energetic particulate solids with 1,2 syndiotactic polybutadiene plus a plasticizer that is miscible with said polybutadiene at a temperature whereat said polybutadiene is molten, melt-casting said molten mixture into a mould, and allowing said molten mixture to cool to a solid high-energy composition with said solid particulates dispersed in plasticized polybutadiene.
  • High molecular weight syndiotactic 1,2 polybutadiene in combination with a suitable plasticizer is found to provide a suitable elastomeric binder system for solid propellant compositions or the like.
  • the polymer is a thermoplastic elastomer which generally melts in the temperature range of from 70°C to 100°C and therefore can be melted in the presence of fuel particulates and oxidizers to form a solvent-free propellant formulation melt.
  • the melt is directly castable as a propellant charge into a rocket motor casing or the like.
  • Polybutadienes in accordance with the present invention preferably have weight average molecular weight of between 100,000 and 200,000.
  • the crystallinities typically range from 10 percent to 35 percent and preferably between 15 and 30%. Densities typically range from 0.90 to 0.91.
  • 1,2 butadiene is meant that substantially all, i.e., greater than 90% of monomer addition is by 1,2 polymerization.
  • syndiotactic is meant that at least 90% of the 1,2 additions result in the pendant vinyl group extending from the side opposite that of the two flanking pendant vinyl groups.
  • Syndiotactic 1,2-polybutadiene polymers suitable for use as binders are sold, for example, by the Japanese Synthetic Rubber Company under the trade designations JSR RB-810, JSR RB-820 and JSR RB-830.
  • Polybutadienes used in accordance with the present invention have thermal properties which make them especially suitable as propellant binders, the range from the brittle point (glass transition temperature (T g )) to the softening point generally encompassing the ordinary ambient temperature range. Viscat softening points of these compounds range from 35°C to 70°C; melting points range from 70°C to 100°C and brittle points range from -35°C to -40°C.
  • T g glass transition temperature
  • Viscat softening points of these compounds range from 35°C to 70°C; melting points range from 70°C to 100°C and brittle points range from -35°C to -40°C.
  • the thermoplastics are elastomers at ambient temperatures, they can be processed as molten plastics at temperatures far below the temperatures where high-energy solids become unstable.
  • the low processing temperatures of 1,2 syndiotactic butadienes is considered an important advantage relative to other thermoplastic elastomers which have been considered for use as propellant
  • the polybutadienes have good tensile properties for binders. 300% moduli range from 40 to 80 kg/cm2; Tensile strengths range from 60 to 140 kg/cm2 and elongation ranges from 650 to 800 %. Shore D hardnesses range from 30 to 50.
  • the complete binder system includes a plasticizer with which the polymer is miscible.
  • Suitable plasticizers include dioctyl adipate (DOA) and dioctyl phthalate (DOP); however, other miscible plasticizers known in the art are also suitable. Mixtures of plasticizers, such as DOA/DOP mixtures are also suitable.
  • Particularly suitable plasticizers are naphthenic oils, such as those sold under the trademark Tufflo by Arco, particularly Tufflo-500.
  • the plasticizer comprises between 50 and 75 percent by weight of the binder system (binder plus plasticizer) and preferably between 50 and 67 percent by weight.
  • the binder system may also include a minor amount of a wetting agent or lubricant, such as lecithin.
  • a wetting agent or lubricant enables a higher solids loading.
  • the lubricant typically comprises up to 4 weight percent of the total weight of the polybutadiene plus plasticizer.
  • a presently preferred lubricant is a coating agent sold under the trade designation FC-430 by 3M.
  • a complete propellant formulation includes a high percentage of energetic solid particulates, including fuel material particulates, such as aluminum, and oxidizer particulates, such as ammonium perchlorate (AP), cyclotetramethylene tetranitramine (HMX) and cyclotrimethylene trinitramine (RDX), the solid particulates typically comprising between 70 and 90 wt. percent of the propellant composition and the balance being substantially all binder system.
  • the propellant may include minor amounts of additional components, such as a bonding agent and burn rate modifiers.
  • the order of mixing propellant formulation ingredients is not considered to be critical. However, for ease of mixing, it is generally preferred that the binder system, including the binder, plasticizer, and any lubricant, be blended under binder melting conditions prior to adding the solids. After the binder system is melted and blended, the solids are added, and mixing is continued to provide a uniform dispersion of solids in binder system. To provide a uniform cast, it is preferred to deaerate the molten formulation and then to cast the melt.
  • Cast propellant may be remelted after solidifying. Thus, there is no need to cast the propellant immediately after mixing, although from an energy efficiency standpoint this is generally desirable.
  • thermoplastic of the propellant composition provides for its eventual recycle, as opposed to the burning required for disposal of thermoset propellant compositions. Because the thermoplastic propellant does not have a "pot life", there are no limitations to the time of casting, and if any problems develop during casting, the process can be delayed as long as necessary merely by maintaining the propellant formulation in molten form.
  • propellants in accordance with the present invention no solvents or other highly volatile substances are required. Accordingly, no special measures or special apparatus are required to contain solvent vapors, to remove solvent from the formulation or to recover solvent for reuse.
  • Propellant formulations in accordance with the present invention may be prepared by conventional mixing apparatus without requiring extrusion, although extrusion may be used to prepare certain forms of propellants, such as propellant pellets.
  • syndiotactic butadienes for use in propellant binders is their low melting temperatures, and propellant formulations using syndiotactic butadienes are processable in the range of to 120°C. Low processing temperatures help to ensure safety in processing high-energy compounds. Syndiotactic butadienes also have excellent low-temperature properties, typically having glass transition temperatures in the range of -40°F (-40°C). Low-temperature properties are important for propellant systems which might be used at very low temperatures or even exposed to very low temperatures prior to use.
  • a pilot scale mix of a composite propellant with a thermoplastic elastomeric binder is described in this example.
  • 240 grams of a composite propellant were made from the following ingredients: Ingredient Weight Percent Syndiotactic Polybutadiene RB-810 8.3 Dioctyl Adipate 15.9 Lecithin 0.8 Unground Ammonium Perchlorate (AP) 200 ⁇ 50.0 Ground Ammonium Perchlorate (AP) 18 ⁇ 25.0 The ingredients were mixed in a Baker Perkins twin blade vertical mixer with a working capacity of approximately 0.5 liters.
  • the propellant was removed from it and cut into 6.35 mm ( 1 4 ⁇ ) diameter by 10.2 cm (4 ⁇ ) long cylindrical stands for testing of burn rate.
  • Four strands were prepared and inhibited on all but one circular face with black enamel paint. These strands were then burned in a pressurized bomb to determine propellant burn rate. Two strands were burned at an average pressure of 6.998 MPa (1015 psig) and had an average burn rate of 6.27 mm/sec (0.247 in/sec). The other two were burned at a pressure of 3.516 MPa (510 psig) and had an average burn rate of 4.65 mm/sec (0.183 in/sec).
  • novel binder system has been described primarily in terms of its use in propellants, the binder system is applicable to other solid, high-energy compositions, such as explosives and gasifiers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (10)

  1. Composition de haute énergie à couler en masse fondue, cette composition comprenant des solides particulaires énergétiques dispersés dans, et spatialement immobilisés dans, un système liant comportant entre 25 et 50 % en poids de polybutadiène-1,2 syndiotactique et entre 50 et 75 % en poids d'un plastifiant miscible audit polybutadiène.
  2. Composition selon la revendication 1 comprenant entre 70 et 90 % de solides particulaires énergétiques, le reste étant formé par ledit système liant.
  3. Composition selon la revendication 1 ou la revendication 2, dans laquelle ledit polybutadiène-1,2 syndiotactique a un poids moléculaire moyen en poids compris entre 100 000 et 200 000.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle ledit plastifiant est choisi parmi de l'adipate de dioctyle, du phtalate de dioctyle et leurs mélanges.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle le système liant comprend jusqu'à 4 % en poids d'un agent mouillant, sur la base du poids total du plastifiant et du polybutadiène dans ledit système liant.
  6. Procédé pour préparer une composition de haute énergie (à grand pouvoir énergétique) comprenant le mélangeage de solides particulaires énergétiques avec du polybutadiène-1,2 syndiotactique, plus un plastifiant qui est miscible audit polybutadiène à une température à laquelle ledit polybutadiène est fondu, la coulée dudit mélange fondu dans un moule, et le fait de laisser ledit mélange fondu refroidir jusqu'à donner une composition solide à haute énergie, dans laquelle lesdits solides particulaires sont dispersés dans le polybutadiène plastifié.
  7. Procédé selon la revendication 6, dans lequel ledit mélange fondu est désaéré avant son refroidissement.
  8. Procédé selon la revendication 7, dans lequel ledit mélange fondu est coulé après désaération et avant son refroidissement.
  9. Procédé selon l'une quelconque des revendications 6 à 8, dans lequel ladite température est au moins égale à 90 °C.
  10. Procédé selon l'une quelconque des revendications 6 à 9, dans lequel on mélange ledit polybutadiène et ledit plastifiant à ladite température, puis l'on ajoute lesdits solides énergétiques.
EP19880302462 1988-03-21 1988-03-21 Compositions de haute énergie à liants thermoplastiques coulables Expired EP0333941B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8888302462T DE3872380D1 (de) 1988-03-21 1988-03-21 Hochenergetische zusammmensetzungen mit einem giessbaren thermoplastischen binder.
EP19880302462 EP0333941B1 (fr) 1988-03-21 1988-03-21 Compositions de haute énergie à liants thermoplastiques coulables

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19880302462 EP0333941B1 (fr) 1988-03-21 1988-03-21 Compositions de haute énergie à liants thermoplastiques coulables

Publications (2)

Publication Number Publication Date
EP0333941A1 EP0333941A1 (fr) 1989-09-27
EP0333941B1 true EP0333941B1 (fr) 1992-06-24

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EP19880302462 Expired EP0333941B1 (fr) 1988-03-21 1988-03-21 Compositions de haute énergie à liants thermoplastiques coulables

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DE (1) DE3872380D1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2714374B1 (fr) * 1993-12-29 1996-01-26 Poudres & Explosifs Ste Nale Compositions pyrotechniques solides à liant thermoplastique et plastifiant polybutadiène silylferrocénique.
AU1703300A (en) * 1998-07-10 2000-02-28 Cordant Technologies, Inc. Improved composite solid propellants including a hydroxy-functional polybutadiene binder and a rocket motor including same
DE102010044344A1 (de) * 2010-09-03 2012-03-08 Rheinmetall Waffe Munition Gmbh Kunststoffgebundene Sprengstoffformulierung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995431A (en) * 1958-06-20 1961-08-08 Phillips Petroleum Co Composite ammonium nitrate propellants containing boron
US4042619A (en) * 1965-05-03 1977-08-16 E. I. Du Pont De Nemours And Company Derivatives of carboxy-terminated polybutadienes
US3986910A (en) * 1974-04-12 1976-10-19 The United States Of America As Represented By The Secretary Of The Navy Composite propellants containing critical pressure increasing additives
DE2529432C2 (de) * 1975-07-02 1985-10-17 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur Herstellung von flexiblen Sprengstoff-Formkörpern
US4384066A (en) * 1980-11-24 1983-05-17 Uniroyal, Inc. Ionic elastomer blends with syndiotactic polybutadiene

Also Published As

Publication number Publication date
DE3872380D1 (de) 1992-07-30
EP0333941A1 (fr) 1989-09-27

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